Preparation of vinyl organo-phosphorous compounds

ABSTRACT

Compounds containing a P-H bond add to hydrocarbon acetylenic unsaturation in the presence of metal coordinating catalysts selected from Groups VIA and VIII of the Periodic Table, to produce unsaturated organophosphorus compounds in good yields. The unsaturated organophosphorus compounds find utility as intermediates for polymerization reactions in the production of flame resistant polymers.

United States Patent Lin June 27, 1972 [54] PREPARATION OF VINYL ORGANO- OTHER PUBLICATIONS PHOSPHOROUS COMPOUNDS Cairns et al., Jour. of American Chem. Soci, Vol. 74, [72] lnventor: Kingso Chingtsung Lin, Newark, Ohio PP- 40 [73] Assignee: Hooker Chemical Corporation, Niagara Primary Examiner joseph Rebold Fans Assistant Examiner-Anton l-l. Sutto [22] Fil d; No ,12, 1969 Attorney-Peter F. Casella, Donald C. Studley, Richard P. n pp No: 876,139 Mueller, James F. Mudd and Richard K. Jackson [57] ABSTRACT [52] g 262 43 Compounds containing a P-l-l bond add to hydrocarbon [51] l t C l 28 acetylenic unsaturation in the presence of metal coordinating [58] a i 6 606/5 P catalysts selected from Groups VIA and Vlll of the Periodic Table, to produce unsaturated organophosphorus compounds [56] Reerences Cited in good yields. The unsaturated organophosphorus compounds find utility as intermediates for polymerization reactions in the production of flame resistant polymers.

8 Claims, No Drawings PREPARATION OF VINYL ORGANO-PI-IOSPIIOROUS COMPOUNDS BACKGROUND OF THE INVENTION The preparation of various unsaturated organophosphorous derivatives has been accomplished by the addition of phosphines and primary or secondary phosphites to acetylenically unsaturated organic compounds activated by an electron withdrawing group under base catalyzed conditions 7 or to acetylenically unsaturated hydrocarbons via free radical catalysis. As indicated by Pudovik et al., Zhur. Ob. Khim., Vol. 31 (1961), pp. 2,480-2,484, the free radical mechanism is operable if the reaction conditions are controlled to stimulate the addition via a radical mechanism. The yields reported by Pudovik et al. for the addition reaction vary from 20 to 57 percent of theory. The addition via the free radical mechanism was said to be anti-Markownikofi.

BRIEF DESCRIPTION OF THE INVENTION In accordance with this invention, it has been discovered that compounds containing a P-H bond add readily to acetylenic unsaturation via the formation of an intermediate coordination compound of the Pl-l ligand or the acetylenic ligand and a metal complexing catalyst selected from the group VIA or VIII of the Periodic Table. In essence, those metals which enter into coordination complexes with acetylenic unsaturation to catalyze the copolymerization or simple polymerization of acetylenic compounds are suitable to use as the catalysts for addition of a reactant containing the P--l-I linkage to acetylenic compounds.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to the catalytic addition of compounds containing a phosphorus-hydrogen (P-H) bond to acetylenic (-C C) compounds to produce a phosphorus-carbon bond in a product having olefinic unsaturation The catalysts found to be effective in the reaction of this invention include salts and complexes of the transition metals which have been employed in the art as the catalysts for the addition and polymerization of acetylenic compounds. The metal salts and their complexes are based upon the metals of Groups VIA and VIII of the Periodic Table. Especially applicable catalysts are the salts of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, osmium and platinum, and their complexes. However, chromium, molybdenum and tungsten salts and their complexes may be employed under proper process conditions as the catalysts for the process of this invention.

The ligands which may be used in the metal complex catalyst for this invention include carbonyl, ammonia, alkylamines, arylarnines, alkylene diamines, arylnitriles, alkylnitriles, oximes,aldimines, ketimines, arylazo compounds, alkylphosphines, arylphosphines, alkylphosphites, arylphosphites, dialkylformamides, and the like. The ionic ligands which may be used in the metal catalyst for this invention are generally any salt of the transition metals, such as halides, carboxylates, sulfonates, phosphites, phosphates, cyanide, phenolates, thiophenolates, imides, alkylphosphides, acetylacetonates, isocyanates, thiocyanates, cyanates, isothiocyanates, and the like.

The formation of a coordination complex between a transition metal and an acetylenically unsaturated reactant may proceed directly or by substitution of the acetylenically unsaturated ligand for a ligand previously coordinated with the metal. For example, platinum and palladium chloride will enter directly into coordination complexes with acetylene. Chromium, molybdenum, tungsten, iron, cobalt, nickel, osmium and irridium form complexes with acetylenic unsaturation usually when other strongly pi-bonding ligands are present.

It is known that acetylene will enter into various types of coordinated complexes with transition metals (Advances In Organo Metallic Chemistry, Vol. 5, 1967, pp. 114-420). It is believed that the complex formation involved in the instant invention is either of the type in which the acetylene becomes bonded to the metal and is still identifiable as such, with the possible loss of one or more of the original ligand groups of the parent molecule, or the complex is the type obtained during the polymerization of acetylenes.

The transition metal salts and their complexes employed in this invention generally form rather stable complexes with acetylenic ligands and a donor molecule containing the phosphorus atom. Because both acetylenic compounds and compounds containing the P-I-I bond are capable of acting as ligands in the formation of coordination compounds with transition metal salts, the catalytic species or the reactive intermediate may be regarded as either one or both of the acetylenic compound and the phosphorus compound complexed through coordination bonds with the transition metal atom. As a result of the pi-bonding between the metal atom and the acetylenic unsaturation, the latter molecule becomes very reactive and susceptible to the addition of a molecule containing a nucleophilic atom.

Although applicant does not desire to be bound by any specific reaction mechanism, it is believed that the reaction of a compound containing a P-H bond with acetylenic unsaturation in the presence of a transition metal salt or complex proceeds by any one of the following paths in which M represents the transition metal, L represents a ligand and n is the umber. Q cqmplsxsd 4 tion occurs. In this sense, the process of the instant invention also presents a technique for stereospecific addition of compounds containing a P-I-I bond to acetylenic unsaturation catalyzed by transition metal complexes to afford a product predominating in the cis-addition product. However, trans-addition may also occur under certain reaction conditions.

Reactants of the type contemplated in the instant invention which contain a PI-l bond are those compounds embraced by the following formula:

in which R is an alkyl group of one to 18 carbon atoms, alkoxy of one to 18 carbon atoms, or aryl of six to 12 carbon atoms. X is oxygen or sulfur, m is from O to 2, n is from to l andp is 3.

More specifically, the reactants contemplated by this invention include phosphine, methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, pentyl phosphine, hexyl phosphine, heptyl phosphine, octyl phosphine, the corresponding dialkyl phosphines, the corresponding alkoxy phosphines and diphenyl phosphine as well as the corresponding primary and secondary phosphites and thio phosphites.

The acetylenically unsaturated reactant for the instant invention may be described by the following formula:

XC I CY in which X and Y are independently selected from the group consisting of hydrogen, alkyl of one to 18 carbon atoms, phenyl and hydroxy substituted alkyl of one to 18 carbon atoms.

The reaction of a compound containing a P-I-I bond with an acetylenically unsaturated compound may be conducted in a suitable inert solvent. Representative inert solvents are the lower alkanols such as methanol, ethanol, propanol, etc; hydrocarbons such as alkanes of five to 18 carbon atoms, benzene, toluene, etc.; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, benzonitrile, etc.; esters such as ethyl acetate, etc.; amides such as dimethyl formamide; and the like. The reaction may be conducted in the absence of a solvent by the application of a suitable pressure to prevent the escape of gaseous reactants The temperature of reaction varies somewhat with the reactants but generally lies between room temperature and 200 C. Preferably the temperature is between 40 to 180 C. Generally, it is preferred that the reaction be conducted in the presence of an inert atmosphere which maybe provided by nitrogen, argon, etc.

The reaction time necessary for a complete reaction will vary somewhat with the reactants, but generally the reaction may be completed within hours. A catalytic amount of the metal complexing agent (0.01 to about 1.0 mole percent) is sufficient to afford a high yield of the addition products. Preferably the amount of the catalyst used is 0.16 to about 0.32 mole percent.

The unsaturated organo-phosphorus compounds resulting from the process of this invention find utility as flame retardant additives for polymers. As such they may be employed in the production of co-polymers with other unsaturated monomers. Furthermore, the products obtained by the process of this invention may be employed as plasticizers or lubricating and hydraulic fluid additives.

The following examples are presented to illustrate various specific embodiments of the instant invention, and are not to,

be construed as representing a limitation on the scope of the invention.

Reference to the transition metals in Groups VIA and VII], of the Periodic Table, supra, is based upon those Groups as they appear in the Handbook of Chemistry and Physics, 32nd Edition, 1950-1951, Chemical Rubber Publishing Company. pp. 336-337.

In the following Examples, the abbreviations are g grams; b.p. boiling point; mrn= millimeters mercury absolute; n,, refractive index; p.p.m. parts per million; n.m.r. nuclear magnetic resonance and m.p. melting point. All the values for IR. analysis are in reciprocal centimeters (cm) and all arm??? a s e sssmisr e 9 W EXAMPLE I Attempted Addition of Di-cyclohexylphosphine to 4-Octyne in the Absence of Catalyst at High Temperature.

A solution of 6.6 g. (0.06 mole) of 4-octyne and 10 g (0.05 mole) of dicyclohexylphosphine in a three-necked flask was heated at for 6 hours. Distillation of the resulting reaction solution gave only the starting materials. The reaction was repeated by heating at 150 for 6 hours. The result gave only the staring materials.

V w EXANIPLEII Addition of Dicyclohexylphosphine to 4-Octyne in the Presence of Dicarbonyldi(triphenylphosphino)Nickel as Catalyst gave:

Fraction I 1.9 g; b.p. 83-95/0.05 mm; dicyclohexylphosphine;

Fraction II 0.5 g; b.p. 95-135/0.05 mm; fore-cut of the Fraction III;

Fraction III 10.7 g; b.p. l43/0.1 mm; dicyclhexyl( 4-octeny1)phosphine. 2.1 g. of distillation residue. Redistillation of Fraction HI gave 9.2 g; b.p. 129l3 l/0.05 mm; n 1.5185. The IR spectrum of the redistilled product showed absorption at 742 (P-C),

888( C=C H) 1,405 (P-C), 1620 (-C C) and 2,950 with shoulder at o=on),

(no PI-l absorption band indicated a tertiary phosphine). The n.m.r. showed a singlet in the vinyl proton region at 7.8 ppm.

Flame photometric analysis:

Found: P, 9.80.

Addition of ch,cii,CH,cH,Pi-i, to 4-Octyne L. is. .7

1,463 (P-C) and 1,615 c c Analysis for c l-l P'l-lgcl z Calculated: C, 41.41; H, 6. Found: C, 41.57; H, 6.34; P

EXAMPLE III Addition of Dicyclohexylphosphine to l-Octyne Using Dicarbonyldi(tripheny1phosphino )Nickel as Catalyst In a 50 ml., three-necked flask equipped with a reflux condenser and a thermometer was placed 10 g. (0.05 mole) of dicyclohexylphosphine and 0.2 g. (33 mole) of dicarbonyldi(triphenylphosphino) nickel. With vigorous stirring, 6.6 g. (0.06 mole) of l-octyne was added to the above solution. The reaction mixture became light brown color and an exothemiic reaction was observed. After heating at 100 for 6 hours, the resulting dark brown solution was distilled to give: 2 5

Fraction 1 5.6 g; b.p. 6783/0.05 mm; dicyclohexyl phosphine;

Fraction II 4.9 g; b.p. l44-148/0.05 mm; light greenish yellow liquid. 4.9 g. of distillation residue.

Upon standing at room temperature, colorless crystals deposited from the Fraction II. The IR spectrum of this colorless crystalline material, m.p. 6266 showed absorption at 2250 (PH) and 1,160 (P 0) (identical as the IR spectrum of dicyclhexylphosphine oxide). Apparently the reaction mixture was partially oxidized by air. The filtrate of Fraction II was redistilled to give 120-l22/0.05 mm; dicyclohexyl( l-octenyl)phosphine. The IR spectrum of this fraction showed absorption at 3,050 (C CH), 1,600 (C C) and 885 (C= CH). 40

Analysis for G l-1 P:

Calculated: P, 10.05; Found: P, 9.86.

EXAMPLE IV Addition of n-butylphosphine to l-pentyne Using (11: 1) 45 Ni(CO) as Catalyst A reaction mixture of 3.4 g (0.05 mole) of l-pentyne, 4.5 g. (0.05 mole) of BuPH and 0.1 g. of (;,P) Ni(C0) in a flask was refluxed on an oil bath at 80 for 18 hours. Distillation of the resulting light brown solution gave:

Fraction I 0.6 g; 40-4ll760 mm; l-pentyne;

Fraction II 0.9 g; b.p. 5759/2.75 mrn; BuPH(C 1-I and 0.9 g. of distillation residue. 2.8 g. (67 percent) of butylphosphine was recovered from an acetone and dry-ice trap.

The infrared spectrum of Fraction 11 showed absorption at 3,050 CH), 2,270 (PH), 1,605 (C C), 1,465 (P-C) E 894 (C F C).

The same reaction was repeated but using an excess of 1- pentyne (3.4 g. (0.05 mole) of l-pentyne, 2.6 g. (0.03 mole) 70 of n-butylphosphine and 0.1 g. of (q5 P) Ni(CO),).

Distillation of the resulting solution gave 0.8 g. of product of W 59497175 "1 3118 E l@? 11479.

EiAMPLE V using as). Ni(CO) as Catalyst Ni(CO) as Catalyst (s )2Ni( )2 n-BuPHz PrO CPr A mixture of 5.5 g. (0.05 mole) of 4-octyne, 4.5 g. (0.05 mole) of n-butylphosphine and 0.1 g. of ((ilgPhNKCO), in a 50 ml. flask was heated at 50 for 10 hours. The reaction solution was distilled to give 7.3 g. of the starting materials. The recovered material (7.3 g.) and 0.2 g. of P) Ni(CO) were again heated at for 2 hours and then at for 1 hour. The reaction mixture became dark brown and was allowed to stand overnight and then distilled: 5.4 g. (75 percent) of clear liquid were obtained at 95-l45/0.05 mm. and 1.2 g. of distillation residue remained. Redisu'llation of 95145/0.05 mm. fraction gave:

Fraction I 1.1 g; 62-95/0.05 mm. Redistillation afforded at 3842/0.025 mm; n 1.4745; n-butyl(4-octenyl)-phosphine.

Fraction H 3.6; 99l0l0.025 mm; n 1.4869; n-butyldi(4-octenyl) phosphine.

Analysis for fraction I C l-l P:

Calculated: C, 71.95; H, 12 .58; P, 15.47; Found: C, 71.82; H, 12.40; P, 15.29. Flame photometric analysis:

Found: P, 15.80. Analysis for fraction 11 C H P:

Calculated C, 77.30; H, 12 .66; P, 9.98; Found: C, 77.17; H, 12.66; P, 9,98

Flame photometric analysis for P gave Found 10.30.

The IR spectrum of Fraction I showed absorption at 2,900

Analysis for C l-l cl PHg:

Calculated: C, 41.27; H, 6. 75; P, 5.32; Found: C, 41.24; H, 6.59; P 5.28.

EXAMPLE VI Addition of n-BuPH t0 l-Octyne Using P) Ni(CO)- as Catalyst A reaction mixture of 4.5 g. (0.05 mole) of n-BuPI-1 5.5 g. (0.05 mole) of l-octyne and 0.1 g. of P) Ni(CO) in a flask was heated at 70-80 for 1.5 hour and at 100 for one additional hour. The reaction mixture became brown in color. The fractional distillation gave 0.75 g; b.p. 5256/0.05 mm; n 1.4700; n-buty1di( l-octenyl)phosphine and 0.32 g; b.p. -160/0.05 mm; n 1.5062; n-butyldi(1-octenyl) phosphine.

EXAMPLEVII Addition of Dim-butylphosphine to 1- Octyne Using 1 To a solution of 14.6 g. (0.1 mole) of dim-butylphosphine and 0.2 g. (3.2 X 10'" mole) of .,P) Ni(CO) was added dropwise 13.5 g. (0.12 mole) of l-octyne with vigorous stirring under an atmosphere of nitrogen at C. The addition of l-octyne was completed in an hour. A total of 6 hours of heating at 145 C. was applied to finish the reaction. The resulting reaction solution was distilled to give, 4.2 g. of l-octyne, 4.3 g. of dibutylphosphine, 16.7 g. (92.5 percent based on dim-butylphosphine) b.p. 70-1002". Redistillation gave 9292.5/0.06 mm; cli-n-butyll-octenylphosphine.

The IR spectra identified C C absorption bands and no Pl-l bond (indicating a tertiary phosphine).

EXAMPLE Vlll Addition of n-Butylphosphine to 3,6-Dimethyl-4-Octyne-3,6- Diol Using P) Ni(CO as Catalyst A reaction mixture of g (0.2 mole) of N-butylphosphine, 34 g. (0.2 mole) of 3,6-dimethyl-4-octyne-3,6-dio1 and 0.2 g. (3.2 X 10" mole) of (I :,P),Ni(CO) in a three-necked flask equipped with a thermometer, a reflux-condenser and a magnetic stirrer was heated at 80 for 1 hour, then at 120 for 8 hours. The color of the reaction mixture became reddish brown. The distillation of the reaction mixture gave:

Fraction 1 9.51 g; b.p. 94-96/760mm; (separated into two layers, 4.9 g. of n-butylphosphine and 4.61 g. of water).

Fraction II 11.0 g; 77-98/ 14 mm unknown product Analysis showed C, 84.10; H, 10.53 and no P.

Fraction Ill 5.15 g; b.p. 6775/0.04 mm; light yellow liquid. Redistillation gave: 71-72/0.05 mm;

*1 1 C4HQPH(C=CHR) where n= :cH2oH. anr 2E2 Analysis for c,,1-1.,Po,=

Calculated: D, 64.58; H, 11 .23; P, 11.90. Found: c, 64.18; H, 11.04; P, 11.60.

Fraction IV 15.6 g; b.p. 75-144/0.04 mm; Redistillation gave a product boiling at 14014l/0.04 mrn. Analysis: C, 64.38; H, 10.81; P, 9.22

EXAMPLE IX Addition of Phenylphosphine to 4-Octyne Using P) Ni(CO) CaHsPHg CH3CH2CH2CECCH2CH2CH3 150 6hrs,

| C 2C 2C a CHzCHzCH;

Analysis for C I-1 1:

Calculated: P, 14.06 Found: P, 14.15

Fraction lll 1.5 g. (10.1 percent); b.p. 110-135/1";

viscous distillate. 1R showed no P-H absorption band but positive identification of a -C C- band.

(CHzCHzCH; CgHrP C=CHCHgCHzCH3 C aC 2C zC 2P z CsHsCEC CaH;

A reaction mixture of 14 g. (0.15 mole) of n-butylphosphine, 27 g. (0.15 mole) of diphenylacetylene and 0.2 g (3.2 X l0" mole) of ((1)3?)QNKCO); was heated over an oil bath at with vigorous stirring. An exothermic reaction was observed. After heating at 135 for 15 minutes, the temperature of the oil bath was maintained at 100 for 4 hours. Distillation of the resulting dark viscous liquid gave:

Fraction 1 3.5 g. (25 percent); b.p. 86-87/760 mm; n-butylphosphine.

Fraction II 12 g. (44 percent); b.p. 101-l08/0.04 mm;

diphenylacetylene.

Fraction III 5.5 g. of the pot residue (24 g.) was distilled under high vacuum to give 3.5 g. of the distillate. The middle cut of the distillate -l73 (coil bath temperature)/1' was analyzed to give C, 73.23; H, 71.58; P, 10.03. IR spectra indicated the presence of a P-l-l absorption band. Therefore calculated for H psi; W

c n p. c, 80.57; 11,788; 1Y1 1.55.

EXAMPLE x1 Addition of PH, to S-decyne Using (q P) Ni(CO) as the Catalyst A suspended solution of 50 g. (0.36 mole) of 5-decyne and 0.5 g. of P) Ni(CO) partially soluble in 5-decyne, was placed in a 300 ml. autoclave. The autoclave was evacuated followed by purging with nitrogen to remove air from the reaction system. Twenty-three grams of PH were charged to the autoclave at room temperature. With vigorous stirring the reaction mixture was heated to C. at 810 psig for 10 hours. The pressure did not drop after heating and standing at room temperature overnight. The autoclave was then pressurized with nitrogen to 1,450 psig at 150 C., and continued heating for- 10 hours. After standing at room temperature overnight the black solid suspended solution was removed from the autoclave, filtered and distilled to give S-decyne and a trace of S-decenylphosphine.

The result of the above reaction indicated that the catalyst used did not dissolve in the solution and partially formed an insoluble Pl-l and Ni(CO) complex. The same reaction was repeated using absolute ethanol as the solvent.

One gram of 1 .,1l-") Ni(CO) was dissolved in a solution of 50 g. of 5-cecyne and 100 g. of absolute ethanol. The solution was then placed in a 300 ml. autoclave and charged with 26.10

g. of PH at room temperature. The autoclave was heated at EXAMPLE XII Reaction of Phosphine with l-heptyne Catalyzed by Ni(ll)- Tl-[PComplexes A reaction mixture of 0.9 g. of NiCl,-6H,O in 100 g. of ethanol, 1.25 g. of tris(hydroxymethyl)phosphine in 50 ml. of water and 24 g. (0.25 mole) of heptyne-l in a 500 ml. threenecked flask was introduced 2.8 g. of phosphine with vigorous stirring at room temperature. The reaction temperature increased to 42 C. (an exothermic reaction) after 35 minutes of introduction of phosphine. The addition of phosphine was completed in 1.5 hours. The reaction solution became dark brown from light brown. The solvent was stripped off under reduced pressure to give a dark colored liquid residue. To this oily residue was added 100 ml. of water, followed by extraction with three 200 ml. portions of diethylether and drying over anhydrous sodium sulfate. The solvent ether was removed to give 25 g. of oily residue which was distilled to give 17.7 g (65 percent) of triheptenylphosphine having a b.p. 125-180C/0.2 mm. Hg.

Analysis for C l-1 ,1:

Calculated: C, 78.21; H, 12 19;P, 9.60 Found: C, 78.08;1-1, 11.85; P, 9.81.

EXAMPLE XIII ll Addition of (C2H50)2P""H to anionic ECCH2CH2CH2 using R=Et or Pr A. Are action mixture of 9.6 g. (0.1 mole) of 3-heptyne, 13.6 g. (0.1 mole) of and 0.2 g. of (d P) Ni(CO) in a Fischer Porter pressure bottle was heated at 180 for 5 hours. Pressure was released once at 100 in order to maintain the pressure lower than 50 psig.

The distillation of the resulting reaction solution gave.

Fraction I 20.5 g. of the starting materials (3073/9.0

mm collected in a dry-ice acetone trap) Fraction II 1.5 g. (6 percent); 871 l8/1 mm and 0.5 g. of distillation residue.

Analysis for C H PO Calculated: P, 13.23;

Flame lhot. Anal. Found: 7 P,

Fractionl 6.5 g; b.p. 31-40/50-9 min; S-heptyn Fraction ll 10.0 g; b.p. 40-78/9 mm;

0 (021150) al -J1 Fraction II] 4.8 g; b.p. 881 12/0.5 mm; m, 1.4501;

and 1.08 g. of light yellow solid residue.

Redistillation of the Fraction lII gave b.p. 69-7210.05 mrn; N 1.4485. IR spectrum of the redistilled product was identical as the reaction product of Experiment A.

EXAMPLE XIV Reaction of Dialkyl Phosphate with 4-octyne using Ni(CO). as Catalyst A reaction mixture of 69 g. of

O z s h l 55 g. of 4-0ctyne and 4.25 g. of Ni(CO) was heated at 150 C. for 8 hours. Distillation of the resulting reaction mixture gave 45.1 g.; b.p. 75-78/l 17 mm; 4-octyne, 49.4 g; b.p. 82 /38 mm;

and 18.8 g; b.p. 80-110/1-0.25 mm; the corresponding phosphonate.

The same reaction was repeated but heated at 180 for 6 hours to give k19 g. (15.8 percent); b.p. 54-55/0.25 mm; unknown product and 89.7 g; b.p. 99-l01/0.25 mm; diethyl 4-octenylphosphonate.

The IR spectrum of the fraction boiling at 99101 C/O.25 mm. was 3,030 cm H 960 oin k959i. @29 29:11:11 E 9HP?EFl- 2,300-2,400 cm. The P NMR spectrum demonstrated one peak at 26 ppm having .1 (P-H) 24 cps which indicated the presence of a cis-addition product,

C3H1 CaHr C 2 s0-P =0 H EXAMPLE XV A reaction mixture of grams (CHaCH2OhI H,

in which R is a member of the group consisting of l-l, alkyl of one to 18 carbon atoms, alkoxy of one to 18 carbon atoms,

and aryl of six to 12 carbon atoms, R and R are members of the group consisting of H, alkyl of one to 18 carbon atoms, hydroxyalkyl of one to 18 carbon atoms, and aryl of six to 12 carbon atoms, X is a member of the group consisting of oxygen and sulfur, m is an integer from to 2, n is an integer from 0 to l, and p is 3, which comprises reacting a compound of the formula;

i l2 ,7 we R W with an acetylenically unsaturated compound of the formula R'C 5 CR" at a temperature between about 20 C. to about 200 C. in the presence of a catalyst selected from the group consisting of dicarbonyl di(triphenylphosphino) nickel, di-(trishydroxymethylphosphino) nickel chloride, di(tri-n-but lph pll s! sm qsiaasyislsqlsatbsnyl- 2. The process of claim 1 in which the temperature of the stionis f m bou 4 Ctto tzoutlBQ. it v V 3. The process of claim 1 in which n is zero and m is zero.

4. The process of claim 1 in which the catalyst is dicarbonyld flriphsn p s hiss n s t a 5. The process of claim 1 in which the catalyst is di-(trists msfl flshesns asla slss shlm- I r 6. The process of claim 1 in which X is oxygen and R is alisfisnslqfi aa flsswt ..,4 7. The process of claim 1 in which the catalyst is di( tri-n-butylphosphino) nickel bromide. 8. The process of claim 1 in which the catalyst is nickel carbonyl.

Po-ww 'UNITED STATES PATENT OFFICE ,(s/ee) V A CERTIFICATE OF CORRECTIGN P tent 673l, 5 we June '27, 1972 Inventoz-(s I H Klngso chingtsung Li n It is certified chat error eppea'zfs in the above-identified patent and that said Letters- Patent are hereby correctedas shown below:

r- Column l, line 5h, column 5, line 35, each occurrence "dicyc lhexyl should read ---d1'c-yclohexyl-l---. Column 5, line 63, "CH" should read --(C=CH)--- and "(P C)=" should read ---(P-C) and-- Column 6, line 76, "1o02" should read ---1oo/2 Column 7, line 1 "c 0'' should read --C=C---; line 76, "-C- C should read -C=C- Column 8, line 7,

should read --n-CL;H l -C=CHC' H- C u .9, l 30, "E Z Z Z" should read ---CCH C CH I I olumn lO, .line 12, 72lO.05" should read ---72/0.05---; line %3, N should read ---n line 36, "M9" should read ------l9--. 1

Signed and sealed this 2nd day'of January 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer a ROBERT GOTTSCHALK I Commlssioner of Patents 

2. The process of claim 1 in which the temperature of the reaction is from about 40* C. to about 180* C.
 3. The process of claim 1 in which n is zero and m is zero.
 4. The process of claim 1 in which the catalyst is dicarbonyldi(triphenylphosphino) nickel.
 5. The process of claim 1 in which the catalyst is di-(tris-hydroxymethylphosphino) nickel chloride.
 6. The process of claim 1 in which X is oxygen and R is alkoxy of one to 18 carbon atoms.
 7. The process of claim 1 in which the catalyst is di(tri-n-butylphosphino) nickel bromide.
 8. The process of claim 1 in which the catalyst is nickel carbonyl. 